Bis (1, 2, 2-trihaloethyl) sulfoxides



United States Patent 3,290,380 BIS(1,2,2-TRIHALOETHYL) SULFOXIDES PaulC. Aichenegg, Prairie Village, Kans, and Carl D. Emerson, Kansas City,Mo., assignors to Chemagro Corporation, New York, N.Y., a corporation ofNew York No Drawing. Original application Jan. 17, 1964, Ser. No.338,297, now Patent No. 3,249,495, dated May 3, 1966. Divided and thisapplication Sept. 8, 1965, Ser.

2 Claims. (Cl. 260-607) This invention relates to new compounds and topesticidal uses thereof.

This application is a division of our c-opending application, Serial No.338,297, filed January 17, 1964, now Patent No. 3,249,495.

It has been proposed to employ bis(2-chloroethyl) sul tone andbis(2-chloroethyl) sulfoxide as fungicides, nematocides and asnon-selective herbicides having both preemergence and post-emergenceactivity, Curtis Patent 3,063,824. As acknowledged by Curtis, suchcompounds are not particularly effective as fungicides and nematocidesbut are more outstanding in their herbicide activity. The compounds ofCurtis, moreover, are formed from fi-chloroethyl sulfide, which is thevery toxic mustard gas. The sulfone of Curtis, moreover, has undesirablevesicant properties. In forming the 'sulf-oxide of Curtis there ispresenta little sulfide or over-oxidized sulfone in the product with theattendant vesicant hazards to humans.

Compounds which have good pre-emergent herbicide activity normally arenot satisfactory as nematocides since there remains the problemofgrowing crops after the killing of the nematodes.

It is an object of the present invention to prepare novel sulfoxides.

Another object is to prepare improved compositions and processes forkilling nematodes.

An additional object is to prepare such compositions without the dangerof having serious vesicant hazards.

A further object is to prepare improved compositions and processes forkilling fungi.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the where each X is ahalogen of atomic weight between 35 and 80, i.e., chlorine or bromine.Examples of such compounds are bis'(1,2,2-trichloroethyl) sulfioxide,bis- (1,2,2-tribromoethyl) sulfoxide, bis 1,2-dichloro-2-brornoethyl)sulfoxide, 1,2,2-trichloroethyl 1,2-di-c'hloro 2'- bromoethyl sulfoxide.The preferred compound is his (1,2,2-trichloroethyl) sulfoxide. It iscritical that the bis(1,2,2-trihaloethyl) sulfoxide be used since whenthe corresponding bis(2,2,2-trihaloethyl) sulfoxide, e.g., bis-(2,2,2-t-richloroethyl) sulfoxide, is employed greatly inferiornematocide and fungicide properties result.

Gbtaining good nematocidal and fungicidal activity thus is not merely aquestion of having a large amount of halogen present. This isfurtherillustrated by the fact that bis(1,2,2,2-tetrachloroethyl) sulfoxide isineffective as a ne-matocide and shows much poorer fungicidal activitythan bis(1,2,2-trichl-oroethyl) sulfoxide.

Compounds such as bis(1,2,2-trichlor0ethyl) sulfoxide appear to exist inseveral modifications, e.g., as a solid and as an oil at roomtemperature. Bot-h modifications are useful as nematccides andfungicides. Neither modification has undesirable vesicant properties.

The compounds of the present invention can be prepared by severalmethods.

(a) By oxidizing a pure ibis(l,2,2-trihaloethyl) sulfide, e.g., withhydrogen peroxide or an organic peroxide such as peracetic acid.

(b) By oxidizing a crude bis(l,2,2-trihaloethyl) sulfide-disulfidemixture and removing sulfinic and sulfonic acids.

The compounds of the present invention also can be reduced to thecorresponding bis(1,2,2-trihaloethyl) sulfides, and this serves as aconvenient way for preparing such pure sulfides since it is difficult toprepare the sulfides in pure form directly by other routes, e.g., (1) byreacting sulfur dichloride with 1,2-dichloroethylene (either cis ortrans or mixtures of cis and trans) or (2) by reacting1,2,2-t-richloroethyl sulfenyl chloride with cis or transdichloroethylene in the presence of aluminum chloride or ferricchloride.

We have been unable to make sulfones corresponding to the sulfoxides ofthe present invention. Procedures for the oxidation of sulfides whichnormally result in sulfone formation in the instant situation stop atthe sulfoxide stage.

Unless otherwise stated, all parts and percentages are by weight.

Example 1 In 800 parts (8.0 moles) of symmetric cis dichloroethylenethere were suspended 10 parts of anhydrous ferric chloride and 204 parts(2.0 moles) of sulfur dichloride were added at 30 to 35 C. over a periodof 2.75 hours. The product was allowed to stand overnight and ferricchloride removed by filtration. The material was washed with diluteaqueous hydrochloric acid and the organic layer dried and the solventremoved by stripping to give 383 parts of a crude mixture ofbis(1,2,2-trichloroethyl) sulfide and bis(1,2,2-trichloroethyl)disulfide. Upon distillation in a high vacuum there was obtained 60.8parts (22.2% yield) of pure bis(1,2,2-trichloroethyl) suifide as ayellow oil B.P. 102 to 108 C., 11 1.5705.

This example was repeated several times using cis, trans or a rnixtureof cis and trans symmetric dichloroethylene and reaction times from 2.5to 3.0 hours. Removal of ferric chloride was also obtained by treatmenttwice with 1 volume of acetone followed by dilution with v2 volumes ofwater fol-lowed by drying. The yields of crude mixtures ranged from 65to 96% and the yield of pure bis(1,2,2-trichloroethyl) sulfide rangedfrom 22 to 28%. The pure compound is identified hereinafter as Compound4975.

Example 2 1 part of aluminum chloride was suspended in 50 parts (0.5mole) of cis-dichloroethylene and 20 parts (0.1 mole) of1,2,-trichloroethyl sulfenyl chloride were added dropwise at 57 C. overa period of 15 minutes. Further heating of the mixture for 1 hour at 60C. completed the reaction. The aluminum chloride catalyst was removed bytreatment with 1 volume of acetone and then 2 volumes of water, theorganic layer dried and then freed of solvent by vacuum stripping. 24.5grams of crude addition product were obtained as a brown oil, n 1.5770.Distillation in a high vacuum gave 15.7 parts (53% yield) ofbis(1,2,2-trichloroethyl) sulfide as a yellow oil B.P. 110 C., 11 1.5736having the same basic infrared Patented Dec. 6, I966 spectrum as theproduct of Example 1. The procedure of Example 2 gave higher yields,e.g., 47 to 74.0% over several different runs, than that of Example 1However, the products of Example 2, on the average, were not as pure asthose of Example 1.

Example 3 Into a suspension of 1 part of ferric chloride 30 parts of cis1,2-dichloroethylene there were added dropwise with stirring 12 parts(0.06 mole) of 1,2,2-trichloroethyl sulfenyl chloride at 60 C. (moderatereflux) over a period of 15 minutes. Standing overnight, removing ferricchloride by using acetone and water, drying of the remaining solutionand removing the organic solvent in vacuum gave 16.3 parts of crudeproduct which, in turn, furnished 7.6 parts (42.5% yield) of purebis(1,2,2-trichloroethyl) sulfide as a yellow oil, B.P. 125 C., 111.5710 when subjected to fractionation in high vacuum.

Example 4 3.1 grams (0.01 mole) of bis(1,2,2-trichloroethyl) sulfoxide(prepared in Example 6) was taken up in a mixture of 20 ml. of glacialacetic acid and 20 ml. of acetic anhydride and reduced by dropwiseaddition under stirring of 15 ml. of a 20% TiCl solution in concentratedhydrochloric acid at room temperature with occasional cooling to controlthe exothermic temperature rise over a period of 30 minutes. The mixturewas then kept for 3 hours at 90 to 95 C. and allowed to stand overnightat room temperature. All operations were carried out in a nitrogenatmosphere. Filtering oif the formed precipitate of titanium dioxide andoxychlorides, diluting the filtrate with 2 volumes of water, taking upthe heavy oil into chloroform, repeated washing free of acid with water,drying and stripping of the solvent gave 2.8 grams (94% yield) of crudebis(1,2,2-trichloroethyl) sulfide, most of which distilled at 90 to 95C. at 0.05 mm. Hg and having the same basic infrared spectrum as theproduct of Example 1.

Example Into 100 parts of a crude mixture of bis(1,2,2-trichloroethyl)sulfide and bis(1,2,2-trichloroethyl) disulfide, made as in Example 1,there were introduced under stirring and occasional cooling by means ofan external ice-water bath at 30 Cfover a period of 1 hour parts of drychlorine gas, sufiicient to convert the 70% disulfide in the crudemixture to easily distillable 1,2,2- trichloroethyl sulfenyl chloride.The resulting mixture was then subjected to fiash evaporation at 0.1 mm.Hg.

- The sulfenyl chloride which came over at 30 to 40 C.

was recovered by trapping and the residue distilled in a high vacuum togive 17 parts of bis(1,2,2-trichloroethyl) sulfide as a yellow oil in ayield of 57%. In other runs yields up to 63% were obtained.

Example 6 62 grams (0.209 mole) of redistilled bis(1,2,2-trichloroethyl) sulfide were oxidized by diluting with 100 ml. ofglacial acetic acid and gradually mixing with 23.7 grams of 30% aqueoushydrogen peroxide (a slight excess) followed by standing at roomtemperature (25 C.) over a period of 42 hours, followed by heating at 60to 70 C. for a further 2 hours. Diluting with 2 volumes of water, takingup the precipitated oil into chloroform, removing free acetic acid byrepeated washing with water, drying and stripping of the solventfurnished a yield of 55 grams (84% yield) of a heavy oil which ondiluting with petroleum ether (Skelly B) and repeated cooling gave 21grams (32% yield) of crude solid product which was recrystallized togive 17 grams (26% yield) of pure white crystals ofbis(1,2,2-trichloroethyl) sulfoxide, M.P. 88 C., B.P. 102 to. 105 C., Cl67.0% (68.0% theory); S 10.0% (theory 10.2% The pure solid product isidentified hereinafter as Compound 4922.

In a repeat of this experiment using a 4 day standing period at roomtemperature for the oxidation the yield of pure product was increased to34%. Low temperatures were also found to diminish the formation ofunsaturated materials as impurities.

Example 7 60 grams (.202 mole) of pure bis(1,2,2-trichloroethyl) sulfidewere diluted with 150 ml. of glacial acetic acid, 20.2 grams of 30%aqueous hydrogen peroxide were added and the mixture allowed to standfor 4 days at room temperature (25 to 27 C.). The mixture was pouredinto 2 volumes of ice-water, the bottom oil taken up with chloroform andthis solution treated as described in Example 6 to give 63.5 grams(quantitative yield) of crude oil, from which after removal of the solidbis(1,2,2-trichloroethyl) sulfoxide by chilling from the petroleum ether(Skelly B) and vacuum stripping gave 34.2 grams (54% yield) ofbis(1,2,2-trichloroethyl) sulfoxide-oil form (i.e., the oilmodification). This was subjected to high vacuum distillation and boiled117 C. to 125 C. at 0.02 to 0.03 mm. Hg and had an 11 1.5602 to 1.5720.About 10 grams of the last fraction obtained in this range had an n1.5720 and was a thick almost colorless syrup. The oil product was thusdivided into two fractions. The lower boiling fraction in the 117 to 125C. range analyzed Cl 66.3%, S 10.6% and the higher boiling fraction inthe 117 to 125 C. range analyzed Cl 66.8%, S 11.6%. (Theory forbis(1,2,2-trichloroethyl) sulfoxide is Cl 68.0%, S 10.2%.) The infraredspectrum for the high boiling oil fraction in Example 7 was very similarto that of the solid product of Example 6, both showing peaks at 3.4microns, about 7.8 microns, 9.3 microns, 9.8 microns, 12.6 microns and13.7 microns. The spectrum for the solid product of Example 6 showed atrace of unsaturated impurity at 109 microns while the spectrum of theoil of Example 7 showed considerably more unsaturated impurity at 10.9microns and also showed unsaturated impurities at 6.4 microns. The highboiling fraction in Example 7 was redistilled and had a B.P. 115 to 117C. This oily modification of his (1,2,2-trichlor0ethyl) sulfoxide isidentified hereinafter as Compound 5008.

-Crystallization of the oily modification of bis(1,2,2- trichloroethyl)sulfoxide prepared in Example 7 could not be achieved in this experimentor in a repeat experiment in which 51% yield of the oily modificationwas obtained.

Example 8 10 grams of ferric chloride (anhydrous) were suspended in 400grams excess) of vinylidene chloride and 102 grams (1.0 mole) of sulfurdichloride were added dropwise under stirring and occasional cooling tomaintain a gentle reflux (35 C.) over a period of 1 hour. Standingovernight, heating to reflux for 3 hours, removing ferric chloride bytreatment with acetone, drying and stripping off excess vinylidenechloride gave 232 grams of crude bis(2,2,2trichloroethyl)sulfide-bis(2,2,2- trichloroethyl) disulfide mixture which was subjectedto fractionation. A 30% yield was obtained of a colorless fraction whichhad a B.P. 91 C., n 1.5642. This Was redistilled to give pure bis2,2,2-trichloroethyl) sul- Iide (Compound 5006) B.P. 88 to 89 C, n1.5551. The product solidified on standing to white needle M.P. 45 C.

Example 9 3.5 grams (0.0118 mole) of bis(2,2,2-trichloroethyl) sulfidewere diluted with 10 ml. of glacial acetic acid and 1.2 grams of 31.0%aqueous hydrogen peroxide (0.011 mole) added. The mixture was allowed tostand for 6 days at room temperature (25 to 30 C.) and diluted withwater to give 3.7 grams (quantitive yield) of the crude product as awhite solid. The latter was taken up in chloroform, washed several timeswith water, dried and stripped to give 1.8 grams (50% yield) ofbis(2,2,2-

trichloroethyl) sulfoxide (Compound 5025) as a white solid which onrecrystallization had a MP. of 135 to 137 C. and a B.P. 0.09 of 143 to144 C.

The compounds of the present invention can be used alone as nematocidesor fungicides but it has been found desirable to apply them to the pest,e.g., to the soil habitat of nematodes, together with inert solids toform dusts, or, more preferably, suspended in a suitable liquid diluent,preferably water. There can also be added surface active agents andinert solids in such liquid formulations. Desirably, 0.05 to 1% byweight of surface active agent is employed. The active ingredient can befrom 0.01 to 95% by weight of the entire composition in such cases.

In place of water there can be employed organic solvents ascarriers,e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, dieseloil, fuel oil, and petroleum naphtha, ketones such as acetone, methylethyl ketone and cyclohexanone, e.g., ethanol, isopropanol and amylalcohol, etc.

The nematocides and fungicides of the present invention can also beapplied with inert nematocidal or fungicidal adjuvants or carriers suchas talc, pyrophyllite, synthetic fine silica. Attaclay, kieselguhr,chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullersearth, cottonseed hulls, wheat flour, soyabean flour, pumice, tripoli,wood flour, walnut shell flour, redwood flour and lignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agents,i.e., wetting agent, are advantageously employed in both the solid andliquid compositions. The surface active agent can be anionic, cationicor nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkyl sulfate salts, alkylamide sulfonatesalts, alkylaryl polyether alcohols, fatty acid esters of polyhydricalcohols and the alkylene oxide addition products of such esters, andaddition products of long chain mercaptans and alkylene oxides. Typicalexamples of such surface active agents include the sodium alkyl benzenesulfonates having 14 to 18 carbon atoms in the alkyl group,alkylphenol-ethylene oxide condensation products, e.g., p isooctylphenolcondensed with ethylene oxide units, soaps, e.g., sodium stearate andpotassium oleate, sodium salt of propylnaphthalene sulfonic acid,(di-Z-ethyl hexyl) ester of sodium sulfosuccinic acid, sodium laurylsulfate, sodium salt of the sulfonated monoglyceride of cocoanut fattyacids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride,octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether,polyethylene esters of fatty acids and rosen acids, e.g., Ethofat 7 and13, sodium N-methyl-N-oleyltaurate, Turkey Red Oil, sodiumdibutylnaphthalene sulfonate, sodium lignin sulfonate (Marasperse N),polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiarydodecyl polyethylene glycol thioether (Nonionic 218), long chainethylene oxide proylene oxide condensation products, e.g., Pluronic 61,sorbitan monolaurate, polyethylene glycol ester of tall oil acids,sodium octylphenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitanmonostearate (Tween 60), sodium dihexyl sulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional methods. Thus, the active ingredient can be mixed with thesolid carrier in finely divided form in amounts small enough to preservethe free-flowing property of the final dust composition.

In commercial practice the compositions containing the nematocides ofthe present invention are applied to the soil infected with nematodes.

In the following examples or tables illustrating nematocidal orfungicidal activity the compounds of the invention as well .as thecomparison compounds were formulated as wettable powders consisting of50% of the compound being tested, 46% Hi-Sil 233 (ultra fine silica),

6 2% Maresperse N (sodium lignin sulfon-ate) and 2% Pluronic L-61(polyethylene oxide-propylene oxide adduct molecular weight about 1000).This wettable powder is hereinatfer designated as Formulation A.

Compound code number: Chemical name The saprophytic nematode tests werecarried out in water as the medium with Panagrellus and Rhabditis spp.at room temperature utilizing Formulation A. The results are recorded aspercent kill at the indicated dosages in parts per million after a 4 dayincubation period. A 10% kill is merely the same amount of kill asoccurs with a blank sample.

TABLE I NESA at ppm. Compound It will be observed that both the oily andsolid modifications of bis(1,2,2-trichloroethyl) sulfoxide were stilleffective saprophytic nematocides at A; the dosage of the closelyrelated bis(2,2,2-trichloroethyl) sulfoxide and at A the dosage ofbis(1,2,2,2-tetrachloroethyl) sulfoxide. It is also apparent thatCompounds 4922 and 5008 are far more nematocidally effective thanCompounds 4242 and 4337.

Compound 4922 was also tested against parasitic nematodes employingFormulation A. The nematode employed was Meloidogyne spp. and theprocedure was a 10 day contact test carried out in a water-agar mediumin the presence of tomato roots at room temperature. The results aregiven on a 010 scale where 0 indicates the presence of severe knotting,i.e., no effectiveness. Compound 4922 rated 10 at 25 ppm. and 5 at 12.5ppm. whereas the remaining compounds of Table I were ineffective at thegiven rates.

Example 11 The compounds were also tested as fungicides in platefungicide tests as indicated in Table II. The compounds were made upinto Formulation A and then added to agar cultures of the fungi. In thetable 10 indicates 100% effectiveness and 0 indicates noeffectiveness.In Table II Py stands for Pythi um spp., Rh for Rhizo'ctonia, F forF-usarium and H for Helsrnintho-sporium. The concentrations areexpressed as parts per million (ppm).

TABLE II Compound QQQUIW 3,290,380 I 7 8 Compounds 4922 and 5008 werealso very effeetiwe 'as 2. Bis(1,2,2-trichloroethyl) sulfoxide. soilfungicides at the rate of (1bs./ acre) of 200, 100, 50, R f C1 d b E 25and 12.5. Compound 4922 was better than 5008 parerences l e y e xammerticularly at rates of 25 lbs./ acre and below. NITED STATES PATENTSiveglalmi d h f 1 (C X CHX) so 5 3,063,824 10/1964 Curtis et a1. 712.7

compoun avlng e orrnu a 2 2 where X is a halogen of atomic weightbetween 35 and CHARLES PARKER Prlmary Examme D. R. PHILLIPS, AssistantExaminer.

1. A COMPOUND HAVING THE FORMULA (CHX2CHX)2SO WHERE X IS A HALOGEN OFATOMIC WEIGHT BETWEEN 35 AND 80.